Basic styryl dyes free from sulphonic acid groups, their production and use

ABSTRACT

Novel basic, styryl dyes containing no sulphonic acid groups and of formula ##SPC1## 
     In which the radicals R, which may be the same or different, signify unsubstituted or substituted hydrocarbon radicals, 
     R 1  signifies an unsubstituted or substituted alkyl radical, 
     Either 
     I. R 6  signifies a hydrogen atom, 
     R 2  signifies an unsubstituted alkyl radical or an alkyl radical substituted by one or more halogen atoms or cyano, aryl or alkoxy radicals, 
     And 
     R 3  signifies an unsubstituted alkyl radical, an alkyl radical substituted by one or more halogen atoms or cyano, aryl or alkoxy radicals, an unsubstituted aryl radical or an aryl radical substituted by one or more halogen atoms or alkyl alloxy or cyano radicals. 
     Ii. R 6  signifies a hydrogen atom, and R 2  and R 3  together with the nitrogen atom to which they are attached signify a saturated or partially saturated, heterocyclic ring of 5 to 7 ring members, 
     Or iii. R 2  signifies an unsubstituted alkyl radical or an alkyl radical substituted by one or more halogen atoms or cyano, aryl or alkoxy radicals, and R 3  and R 6 , together with the nitrogen atom and carbon atom to which they are attached and the carbon to which the nitrogen atom is attached, signify a saturated or partially saturated, heterocyclic ring of 5 to 7 ring members, 
     X. R 4  signifies a hydrogen atom or an unsubstituted or substituted alkyl radical, and R 5  signifies an unsubstituted or substituted alkyl or aryl radical, 
     Or y. R 4  and R 5 , together with the nitrogen atom to which they are attached, signify a saturated or partially saturated, heterocyclic ring of 5 to 7 ring members, 
     R 7  signifies a hydrogen or halogen atom, or an unsubstituted or substituted alkyl radical, 
     A n   -   signifies an anion, 
     And the rings B and D may optionally be further substituted by one or more non-water-solubilizing substituents. 
     The dyes are useful for dyeing polyacrylonitrile, acrylonitrile copolymer, synthetic polyamide and polyester fibres, modified by the introduction of acid groups, plastic materials, synthetic and natural resins, leather and paper.

This is a continuation, of application Ser. No. 215,195 filed Jan. 3,1972, and now abandoned.

This invention relates to basic, styryl dyes, which contain no sulphonicacid groups.

More particularly, this invention provides basic, styryl dyes containingno sulphonic acid groups and of formula I, ##SPC2##

in which the radicals R, which may be the same or different,

Signify unsubstituted or substituted hydrocarbon radicals,

R₁ signifies an unsubstituted or substituted alkyl radical,

Either i. R₆ signifies a hydrogen atom,

R₂ signifies an unsubstituted alkyl radical or an alkyl radicalsubstituted by one or more halogen atoms or cyano, aryl or alkoxyradicals,

And R₃ signifies an unsubstituted alkyl radical, an alkyl radicalsubstituted by one or more halogen atoms or cyano, aryl or alkoxyradicals, an unsubstituted aryl radical or an aryl radical substitutedby one or more halogen atoms or alkyl, alkoxy or cyano radicals,

ii. R₆ signifies a hydrogen atom, and R₂ and R₃ together with thenitrogen atom to which they are attached signify a saturated orpartially saturated, heterocyclic ring of 5 to 7 ring members,

iii. R₂ signifies an unsubstituted alkyl radical or an alkyl radicalsubstituted by one or more halogen atoms or cyano, aryl or alkoxyradicals, and R₃ and R₆, together with the nitrogen atom and carbon atomto which they are attached and the carbon to which the nitrogen atom isattached, signify a saturated or partially saturated, heterocyclic ringof 5 to 7 ring members,

either x. R₄ signifies a hydrogen atom or an unsubstituted orsubstituted alkyl radical, and R₅ signifies an unsubstituted orsubstituted alkyl or aryl radical,

or y. R₄ and R₅, together with the nitrogen atom to which they areattached, signify a saturated or partially saturated heterocyclic ringof 5 to 7 ring members,

R₇ signifies a hydrogen or halogen atom, or an unsubstituted orsubstituted alkyl radical,

A^(n) ⁻ signifies an anion,

n signifies 1, 2 or 3,

and the rings B and D may optionally be further substituted by one ormore non-water-solubilising substituents.

Suitable hydrocarbon radicals for R in formula I, include unsubstitutedand substituted alkyl, cycloalkyl of 5 to 7 ring carbon atoms and arylradicals, for example a cyclohexyl, alkylcyclohexyl or phenyl radical.

Where two substituents in formula I combine with adjacent atoms to forma heterocyclic ring, suitable heterocyclic rings include pyrrolidine,piperazine, morpholine, aziridine and piperidine rings.

As used herein, the term alkyl signifies a straight or branched chainalkyl radical of 1 to 12, suitably 1 to 6 and preferably 1 to 4 carbonatoms. Suitable substituted alkyl radicals include alkyl radicalssubstituted by one or more halogen atoms, or hydroxyl, cyano or arylradicals. Preferred aryl substituted alkyl radicals, i.e. aralkylradicals include the benzyl radical. Suitable aryl radicals include thephenyl radical.

As used herein, the term alkoxy signifies an alkoxy radical of 1 to 6,preferably 1 to 3 carbon atoms.

As used herein, the term halogen signifies bromine, fluorine, iodine or,preferably, chlorine.

The anion A^(n) ⁻ may suitably be an inorganic or organic anion, such asa halide, e.g. chloride, bromide or iodide, sulphate, disulphate,methylsulphate, aminosulphonate, perchlorate, carbonate, bicarbonate,phosphate, phosphorus molybdate, phosphorus tungstate, phosphorustungstic molybdate, benzenesulphonate, naphthalene, sulphonate,4-chlorobenzenesulphonate, oxalate, maleate, malate, acetate,propionate, lactate, succinate, chloracetate, tartrate,methanesulphonate, or benzoate ion, or a complex anion, such as that ofzinc chloride double salts.

Preferred dyes of formula I include those in which each radical Rsignifies a methyl radical, in particular those of formula Ia, ##SPC3##

in which

R₁ ' signifies a methyl or ethyl radical,

R₂ ' signifies an unsubstituted alkyl radical, an alkyl radicalsubstituted by one or more halogen atoms or cyano groups, or a benzylradical,

and R₃ ' signifies an unsubstituted alkyl radical, an alkyl radicalsubstituted by one or more halogen atoms or cyano radicals, a benzylradical, an unsubstituted aryl radical, or an aryl radical substitutedby one or more halogen atoms or alkyl or alkoxy groups,

and A^(n) ⁻ and n are as defined above.

The invention also provides processes for the production of the dyes offormula I, characterized by

a. reacting a compound of formula II, ##SPC4##

in which R, R₁, R₄, R₅ and ring B are as defined above, or a compound offormula III, ##SPC5##

in which R, R₁, R₄, R₅, A^(n) ⁻, n and ring B are as defined above, witha compound of formula IV, ##SPC6##

in which R₂, R₃, R₆, R₇ and ring D are as defined above, provided that,when a compound of formula II is employed, the reaction is eithercarried out in the presence of, or the product resulting from reactionbetween the compounds of formula II and IV is treated with, an acid offormuula V,

    h -- a                                                     v

in which A signifies a radical convertible into an anion A^(n) ⁻, asdefined above, or

b. quaternising a compound of formula VI, ##SPC7##

in which R, R₂, R₃, R₄, R₅, R₆, R₇ and rings A and B are with anappropriate quaternising agent, and, where required, converting theanion A^(n) ⁻ in a resulting product into another anion A^(n) ⁻.

Process (a) is suitably carried out at a temperature of from 50° to 130°C, preferably 70° to 100° C, and in the presence of an organic solvent,e.g. acetic acid. Where a compound of formula II is reacted with acompound of formula IV in the presence of an acid of formula V, thelatter may, if appropriate, e.g. when it is acetic acid, serve as thesolvent. Alternatively, where the acid V is a mineral acid, the solventmay comprise a mixture of water and an organic solvent.

The quaternisation in process (b) may be carried out in conventionalmanner, for example in an inert solvent, in an aqueous suspension, oralternatively, and where appropriate, by employing an excess of thequaternising agent to provide a reaction medium. The process may, ifnecessary, be carried out at an elevated temperature and in a bufferedmedium, provided suitably by an organic acid and, if necessary, a base.Suitable quaternising agents include compounds of formula R₁ A, in whichR₁ and A are as defined above. Particular quaternising agents includealkyl halides, such as ethyl chloride, bromide or iodide, alkylsulphates, such as dimethyl sulphate, benzyl chloride, acrylic amidehydrohalides, e.g. CH₂ =CH--CO--NH₂.HCl, chloroacetic alkyl esters,β-chloropropionic acid amides, epoxides, such as ethylene oxide andpropylene oxide, and epichlorohydrin.

Where required, the anion A^(n) ⁻ in a resulting product may beconverted into a different anion in conventional manner, for example bymeans of an ion exchanger, or by reaction with salts or acids, ifnecessary in more than one step, e.g. via the hydroxide or bicarbonate.

The resulting compounds of formula I may be isolated and purified usingconventional techniques.

The compounds of formula II, III, IV, V and VI are either known or maybe produced in conventional manner from available materials.

The dyes of the invention are suitable for the exhaust or pad dyeing andprinting of polyacrylonitrile and acrylonitrile copolymer fibres inloose form, as yarn and in the various textile forms, and for dyeing thecomponent of such fibres in blends, e.g. yarns and fabrics, with otherfibres. They may also be used for exhaust and pad dyeing and printingsynthetic polyamide and synthetic polyester fibres modified by theintroduction of acid groups, such as those described in Belgian Pat. No.706,104 and U.S. Pat. Nos. 3,018,272 and 3,379,723. The present dyes mayalso be used for dyeing leather and paper.

The dyes of the present invention have good solubility in organicsolvents and are suitable for the coloration of plastic materials andsynthetic and natural resins, in the presence or absence of solvents.

In exhaust dyeing, the dyes may suitably be applied from neutral or acidaqueous media, and at a temperature of from 60° to 100° C, or at atemperature above 100° C and under pressure. Level dyeings may beobtained without the assistance of retarders.

The dyes of the present invention may advantageously be used alone, inadmixture, or in admixture with other basic, cationic dyes.

Dyeing with the dyes of the present invention, particularly onpolyacrylonitrile and acrylonitrile copolymer fibres, generally resultsin level dyeings which have good fastness to light and wet treatments,such as washing, water, sea water, dry cleaning, crossdyeing andsolvents, and also to sublimation, pleating and decatizing. The dyes arewell soluble, particularly in water, and show good stability to salt andpH conditions. They reserve natural and synthetic polyamide fibres andtheir stability to lengthy dyeing times at the boil is noteworthy.

The dye of formula VII, ##SPC8##

is described in United States Pat. No. 2,242,474 for the dyeing ofpolyacrylonitrile. The present dyes show improved light-fastnessproperties on polyacrylonitrile fibres, over this dye.

Furthermore, the dyes of the present invention are faster to light onacid modified, i.e. basic dyeable, polyester fibres, than the dye offormula VIII, ##SPC9##

which is described in United States Pat. No. 2,350,393.

The following Examples, in which all parts and percentages are by weightand all temperatures are in degrees Centigrade, illustrate theinvention.

EXAMPLE 1 [process a)]

280 Parts of 5-N,N-dimethylsulphonamido-1,3,3-trimethyl-2-methyleneindoline are stirred into 275 parts of acetic acid, and 216 parts of thealdehyde of the formula XI, ##SPC10##

are introduced into the solution. The violet-coloured mixture is raisedto 50°-55° and stirred at this temperature for 3 hours. Over the courseof the next hour, the reaction mixture is added to a solution of 300parts of common salt and 2500 parts of water. Stirring is continued for2 hours while the dye formed, which is of the formula XII, ##SPC11##

settles out. It is isolated by filtration and washed with a littlebrine. This water-soluble dye gives dyeings of red-violet shade onpolyacrylonitrile and acrylonitrile copolymer fibres, which have goodlight and wet fastness properties.

EXAMPLE 2 [process a)]

To a solution of 280 parts of5-N,N-dimethylsulphonamido-1,3,3,-trimethyl-2-methylene indoline in 350parts of acetic acid, are added 241 parts of the aldehyde of the formulaXIII, ##SPC12##

The blue-violet mixture is raised to 80°-90° and reacted for 2 hours atthis temperature with stirring. The reaction mixture is diluted with2500 parts of water, and 250 parts of common salt and 75 parts of zincchloride are then added to precipitate the dye of the formula XIV,##SPC13##

The mixture with the precipitated dye is stirred for a further 2 hours,after which the dye is filtered and washed with brine. The resulting dyedissolves in water and gives dyeings of violent shade onpolyacrylonitrile and acrylonitrile copolymer fibres, which show goodlight and wet fastness.

The structural composition of further dyes is shown in Table T below.They are produced by the procedure of Example 1 or 2 and are of theformula IX, ##SPC14##

where R₂₀, R₂₁, R₂₂ and R₂₃ have the significance indicated in the tableand,

A^(n) ⁻ and n are as defined above, A^(n) ⁻ may in particular be any ofthe specific anions hereinbefore mentioned.

                                      TABLE T                                     __________________________________________________________________________    Example                                                                            R.sub.20                                                                          R.sub.21                                                                          R.sub.22  R.sub.23 Shade of dyeing on                            No.                             polyacrylonitrile fiber                       __________________________________________________________________________     3   --CH.sub.3                                                                        H   --CH.sub.3                                                                              --CH.sub.3                                                                             bluish red                                     4   "   H   --C.sub.2 H.sub.5                                                                       --C.sub.2 H.sub.5                                                                      red-violet                                     5   "   H   --C.sub.3 H.sub.7                                                                       --C.sub.3 H.sub.7                                                                      "                                              6   "   H   --C.sub.4 H.sub.9                                                                       --C.sub.4 H.sub.9                                                                      "                                              7   "   H   --C.sub.2 H.sub.4 Cl                                                                    --CH.sub.3                                                                             "                                              8   "   H   --C.sub.2 H.sub.4 Cl                                                                    --C.sub.2 H.sub.5                                                                      "                                              9   "   H   --C.sub.2 H.sub.4 --CH                                                                  --CH.sub.3                                                                             bluish red                                    10   "   H   --C.sub.2 H.sub.4 --CH                                                                  --C.sub.2 H.sub.5                                                                      "                                             11   "   H   --C.sub.2 H.sub.4 --CH                                                                  --C.sub.2 H.sub.4 cN "                                 12   "   H   --C.sub.2 H.sub. 4 Cl                                                                   --C.sub.2 H.sub.4 Cl                                                                   red-violet                                    13   "   H   --CH.sub.2 C.sub.6 H.sub.5                                                              --CH.sub.3                                                                             bluish red                                    14   "   H   --CH.sub.2 --C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.5                                                                      "                                             15   --CH.sub.3                                                                        H   --CH.sub.2 --C.sub.6 H.sub.5                                                            --CH.sub.2 --C.sub.6 H.sub.5                                                           bluish red                                    16   "   H   --CH.sub.2 --C.sub.6 H.sub.4 --Cl                                                       --C.sub.2 H.sub.5                                                                      "                                             17   "   H   --CH.sub.2 --CH--CN                                                                     --C.sub.2 H.sub.5                                                                      "                                                          |                                                                    CH.sub.3                                                         18   "   H   --CH.sub.3                                                                              --C.sub.6 H.sub.5                                                                      violet                                        19   "   H   --C.sub.2 H.sub.5                                                                       --C.sub.6 H.sub.5                                                                      "                                             20   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --CH.sub.3                                                       "                                                                        21   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --CH.sub.3                                                       "                                                                        22   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --Cl                                                             red-violet                                                               23   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --Cl                                                             "                                                                        24   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --CN                                                             "                                                                         25.sup.c                                                                          "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                               violet                                                                   26   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                               "                                                                        27   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --OCH.sub.3                                                      "                                                                        28   "   H   --CH.sub.2 --C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.4 CN                                                                   bluish red                                     29.sup.d                                                                          "   --CH.sub.3                                                                        --CH.sub.3                                                                              --CH.sub.3                                                                             red-violet                                    30   "   "   --C.sub.2 H.sub.5                                                                       --C.sub.2 H.sub.5                                                                      "                                             31   "   "   --C.sub.2 H.sub.4 Cl                                                                    --C.sub.2 H.sub.5                                                                      "                                             32   "   "   --C.sub.2 H.sub.4 CN                                                                    --CH.sub.3                                                                             "                                             33   "   "   --C.sub.2 H.sub.4 CN                                                                    --C.sub.2 H.sub.4 --CN                                                                 "                                             34   "   "   --C.sub.2 H.sub. 4 Cl                                                                   --C.sub.2 H.sub.4 Cl                                                                   "                                             35   "   "   --CH.sub.2 --C.sub.6 H.sub.5                                                            --CH.sub.3                                                                             "                                             36   "   "   --CH.sub.2 --C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.5                                                                      "                                             37   "   "   --CH.sub.2 --C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.4 CN                                                                   "                                             38   "   "   --CH.sub.2 --C.sub.6 H.sub.5                                                            --CH.sub.2 --C.sub.6 H.sub.5                                                           "                                             39   --CH.sub.3                                                                        --CH.sub.3                                                                        --CH.sub.3                                                                              --C.sub.6 H.sub.5                                                                      violet                                        40   "   "   --C.sub.2 H.sub.5                                                                       --C.sub.6 H.sub.5                                                                      "                                             41   "   "   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --Cl                                                             "                                                                        42   "   "   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --CH.sub.3                                                       "                                                                        43   "   "   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --OCH.sub.3                                                      "                                                                        44   "   "   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                               "                                                                        45   "   "   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --OCH.sub.3                                                      "                                                                        46   "   "   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                               "                                                                        47   "   "   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --CH.sub.3                                                       "                                                                        48   --C.sub.2 H.sub.5                                                                 H   --CH.sub.3                                                                              --CH.sub.3                                                                             bluish red                                    49   "   "   --C.sub.2 H.sub.5                                                                       --C.sub.2 H.sub.5                                                                      red violet                                    50   "   H   --C.sub.2 H.sub. 4 Cl                                                                   --C.sub.2 H.sub.5                                                                      "                                             51   "   H   --C.sub.2 H.sub.4 CN                                                                    --CH.sub.3                                                                             bluish-red                                    52   "   H   --C.sub.2 H.sub.4 CN                                                                    --C.sub.2 H.sub.5                                                                      "                                             53   "   H   --C.sub.2 H.sub.4 CN                                                                    --C.sub.2 H.sub.4 CN                                                                   "                                             54   "   H   --C.sub.2 H.sub.4 Cl                                                                    --C.sub.2 H.sub.4 Cl                                                                   "                                             55   "   H   --CH.sub.2 --C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.5                                                                      "                                             56   "   H   --CH.sub.2 --C.sub.6 H.sub.5                                                            --CH.sub.2 --C.sub.6 H.sub.5                                                           "                                             57   "   H   --CH.sub.2 --C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.4 --CN                                                                 "                                             58   --C.sub.2 H.sub.5                                                                 H   --CH.sub.3                                                                              --C.sub.6 H.sub.5                                                                      violet                                        59   "   H   --C.sub.2 H.sub.5                                                                       --C.sub.6 H.sub.5                                                                      "                                             60   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --CH.sub.3                                                       "                                                                        61   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 -- CH.sub.3                                                      "                                                                        62   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --Cl                                                             red-violet                                                               63   --C.sub.2 H.sub.5                                                                 H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --Cl                                                             red-violet                                                               64   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --OCH.sub.3                                                      violet                                                                   65   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --OCH.sub.3                                                      "                                                                        66   "   H   --CH.sub.3                                                       p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                               "                                                                        67   "   H   --C.sub.2 H.sub.5                                                p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                               "                                                                        68   --CH.sub.3                                                                        --CH.sub.3                                                                        --C.sub.2 H.sub.4 --CN                                                                  --C.sub.2 H.sub.5                                                                      red-violet                                    __________________________________________________________________________     ##SPC15##

In the following Table T₁, the structural composition of further dyes isgiven. They can be produced in accordance with the procedure of Example1 or 2 and are of formula X, ##SPC16##

in which R₄, R₅ and R₂₀ to R₂₃ are as defined in the table, and A^(n) ⁻and n are as defined above. A^(n) ⁻ may, for example, be any of thespecific anions hereinbefore mentioned.

                                      TABLE T.sub.1                               __________________________________________________________________________                                        Shade of dye-                                                                ing on poly-                               Exp                                acrylonitrile                              No.                                                                              R.sub.4                                                                           R.sub.5                                                                           R.sub.20                                                                          R.sub.21                                                                          R.sub.22                                                                             R.sub.23 fiber                                      __________________________________________________________________________    69 --C.sub.2 H.sub.5                                                                 --C.sub.2 H.sub.5                                                                 --CH.sub.3                                                                        H   --CH.sub.3                                                                           --CH.sub.3                                                                             red-violet                                 70 "   "   "   --CH.sub.3                                                                        --CH.sub.3                                                                           --CH.sub.3                                                                             reddish-violet                             71 "   "   "   "   --C.sub.2 H.sub.4 CN                                                                 --C.sub.2 H.sub.5                                                                      red-violet                                 72 "   "   "   H   --CH.sub.3                                                 p-C.sub.6 H.sub.4 --OCH.sub.3                                                    violet                                                                     73 "   "   "   H   --CH.sub.3                                                 p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                             violet                                                                     74 "   "   "   H   --C.sub.2 H.sub.5                                                                    --C.sub.2 H.sub.5                                                                      red-violet                                 75 "   "   "   --CH.sub.3                                                                        --C.sub.2 H.sub.5                                                                    --C.sub.2 H.sub.5                                                                      reddish-violet                             76 --C.sub.6 H.sub.5                                                                 --H "   H   --CH.sub.3                                                                           --CH.sub.3                                                                             red-violet                                 77 "   H   "   H   --C.sub.2 H.sub.5                                                                    --C.sub.2 H.sub.5                                                                      red-violet                                 78 "   H   "   H   --C.sub.2 H.sub.4 CN                                                                 --CH.sub.3                                                                             red-violet                                 79 "   H   "   H   --C.sub.2 H.sub.4 CN                                                                 --C.sub.2 H.sub.5                                                                      red-violet                                 80 "   H   "   H   --CH.sub.3                                                 p-C.sub.6 H.sub.4 --OCH.sub.3                                                    violet                                                                     81 "   H   "   H   --CH.sub.3                                                 p-C.sub.6 H.sub.4 --OC.sub.2 H.sub.5                                             violet                                                                     82 "   H   "   --CH.sub.3                                                                        --CH.sub.3                                                                           --CH.sub.3                                                                             red-violet                                 83 "   H   "   --CH.sub.3                                                                        --C.sub.2 H.sub.5                                                                    --C.sub.2 H.sub.5                                                                      violet                                     84 "   H   "   "   --C.sub.2 H.sub.4 CN                                                                 --C.sub.2 H.sub.5                                                                      violet                                     85 "   H   "   "   --C.sub.2 H.sub.4 Cl                                                                 --C.sub.2 H.sub.5                                                                      red-violet                                 86 --C.sub.2 H.sub.5                                                                 --C.sub. 2 H.sub.5                                                                "   "   --C.sub.2 H.sub.4 Cl                                                                 --C.sub.2 H.sub.5                                                                      red-violet                                 87 "   "   "   H   --C.sub.2 H.sub.4 CN                                                                 --CH.sub.3                                                                             red-violet                                 88 "   "   "   H   --C.sub.2 H.sub.4 CN                                                                 --C.sub.2 H.sub.5                                                                      red-violet                                 89 "   "   "   H   --C.sub.2 H.sub.4 CN                                                                 --C.sub.2 H.sub.4 CN                                                                   red-violet                                 __________________________________________________________________________

EXAMPLE 90:

A mixture of 20 parts of the dye of Example 1 and 80 parts of dextrin isground in a ball mill for 48 hours. One part of the resultingpreparation is pasted with 1 part of 40% acetic acid and 400 parts ofdistilled water are added at 40° to the paste, with stirring and boilingto dissolve. The solution is added to 7600 parts of distilled water,with the addition of 2 parts of glacial acetic acid.

100 parts of a fabric of polyacrylonitrile fibre are introduced intothis dyebath at 60°, after pretreatment for 10-15 minutes at 60° in abath of 8000 parts of water containing 2 parts of glacial acetic acid.The dyebath is raised to 100° over 30 minutes and held at the boil for 1hour. On removal, the fabric is rinsed. A level red-violet dyeing isobtained which has good light and wet fastness properties.

What is claimed is:
 1. A compound of the formula ##SPC17##wherein R₂₀ ismethyl or ethyl, R₂₁ is hydrogen or methyl, R₂₂ is methyl or ethyl, R₂₃is phenyl monosubstituted in the para position by methyl, methoxy,ethoxy, chloro, or cyano, A^(n) ⁻ is an anion, and n is 1, 2 or
 3. 2. Abasic styryl dye according to claim 1, of formula, ##SPC18##
 3. A basic,styryl dye according to claim 1, of formula ##SPC19##